CN1084395C

CN1084395C - Improved method for electrolysis of aqueous solutions of hydrochloric acid

Info

Publication number: CN1084395C
Application number: CN97102270A
Authority: CN
Inventors: G·法塔
Original assignee: De Nora Permelec SpA
Current assignee: Denuola Electrochemical Technology Co.,Ltd.; Uhdenora Technologies SRL
Priority date: 1996-01-19
Filing date: 1997-01-17
Publication date: 2002-05-08
Anticipated expiration: 2017-01-17
Also published as: BR9700712A; DE69707320D1; CA2194115A1; RU2169795C2; EP0785294B1; JP3851397B2; TW351731B; PL185834B1; CA2194115C; CN1172868A; PL317988A1; ITMI960086A1; HUP9700038A3; HUP9700038A2; IT1282367B1; HU9700038D0; MX9700478A; ITMI960086A0; US5770035A; DE69707320T2

Abstract

The improved method for the production of chlorine from aqueous solutions of hydrochloric acid in a membrane electrolysis cell comprises a cathode compartment equipped with a gas diffusion cathode fed with air or enriched air or oxygen and an anodic compartment with an anode provided with an electrocatalytic coating for chlorine evolution. Said anode compartment is fed with an aqueous solution of hydrochloric acid having a maximum concentration of 20% and a maximum temperature of 60 DEG C, and containing an oxidizing compound having a redox potential of at least 0 Volts NHE and preferably 0.3-0.6 Volts NHE. A suitable oxidizing compound is trivalent iron in concentrations comprised in the range of 100-10,000 ppm. Both the anodic and cathodic compartment of the cell and their internal structures are made of titanium or alloys thereof, such as 0.2%. titanium-palladium The parts made of titanium in which crevices may be present are provided with a protective coating based on metals of the platinum group, their oxides as such or as a mixture of the same.

Description

Method for electrolyzing aqueous solution of hydrochloric acid

The invention relates to a method for producing chlorine by electrolyzing hydrochloric acid aqueous solution.

The modern chemical industry is largely based on the use of chlorine as a feedstock. Reactions of practical interest can be divided into two classes depending on whether the final product contains chlorine:

A. the final product contains chlorine

A1. Polyvinyl chloride (PVC) is produced by polymerization of Vinyl Chloride Monomer (VCM). VCM from ethylene

And chlorine to Dichloroethane (DCE) and then from the thermal cracking of DCE to vinyl chloride in a two-step process, the reaction being as follows:

hydrochloric acid, which is a by-product of the reaction, corresponds to 50% of the chlorine used and can be reconverted to DCE by oxychlorination using oxygen as follows:

on the contrary, in some other industrial processes, the hydrochloric acid cannot be recycled, and its commercialization is questioned in the case of markets where the general demand is modest, also taking into account the content of chlorinated organic impurities. These typical methods are as follows.

A2. Production of chlorobenzene

A3. Production of methyl chloride

Methyl chloride can be used as a starting material for the production of fluorinated compounds by exchange with hydrofluoric acid:

B. the final product contains no chlorine

Typically, polyurethanes are produced from the isocyanate starting reactant by a two-step reaction:

although in the chlorination process in A) the hydrochloric acid contains 50% of the chlorine used, all chlorine is discharged as by-product hydrochloric acid for the production of isocyanates. The same holds true forIs used for the production of polyisocyanates.

Similar characteristics are also present in the production of titanium dioxide. Chlorine is used to produce titanium tetrachloride which is then converted to titanium dioxide with the co-production of hydrochloric acid.

With the development of the chemical industry, the construction of new plants for the production of isocyanates and fluorinated compounds in addition to certain chlorinated compounds and the expansion of existing plants is immediately promoted, so that it can be easily foreseen that large amounts of hydrochloric acid are available, even if the market demand is very limited. In view of the above, it would appear to be of great interest to have available a process for converting hydrochloric acid to chlorine.

The technical background concerning the conversion of hydrochloric acid into chlorine can be gathered as follows: catalytic processes these processes are obtained by the well-known Deacon process, invented at the end of the 19 th century, which is based on the oxidation of gaseous hydrochloric acid over a solid catalyst (cupric chloride):

this process is recently significantly improved by the optimisation of chromium oxide containing catalysts and by operating at considerably lower temperatures. A problem affecting this process is the thermodynamics of the reaction, which only partially converts hydrochloric acid. Therefore, downstream of the reaction, the process necessitates two processes, separation of chlorine from hydrochloric acid and recycling of unconverted hydrochloric acid. In addition, the aqueous phase discharged by the apparatus (water being the reaction product) contains heavy metals released by the catalyst. To overcome these drawbacks, it has recently been proposed to carry out a two-step oxidation, i.e. a reaction between gaseous hydrochloric acid and copper oxide to produce copper chloride, followed by a reaction between copper chloride and oxygen to produce chlorine and copper oxide, which is then subjected to the first step of reaction ("chemical engineering news", 9/11/1995 edition). However, this new process involves the need to optimize the catalysts so that they can withstand thermal shock and attrition. Electrochemical process hydrochloric acid in the form of an aqueous solution is electrolyzed in an electrochemical cell divided into two compartments by means of a porous diaphragm or an ion exchange diaphragm of the perfluorinated type. The following reactions were carried out at both electrodes (anode and cathode):

the overall reaction:

this process has been used in some industrial production plants. In an optimized variant, the process consumes 1500 kWh/ton of chlorine and has a current density of 4000A/m². This energy consumption is generally considered to be too high to be economically attractive and also due to the high investment costs. In fact, the strong corrosiveness of hydrochloric acid solutions and chlorine gases requires the choice of graphite as the construction material, and machining requires high costs. In addition, graphite is extremely brittle and therefore the reliability of the apparatus is a problem, in particular it is not possible to operate under pressure, but there may be a clear advantage in terms of product quality and the combination of electrolysis process and production apparatus. Graphite today can be replaced by graphite composites obtained by hot pressing graphite powder with a chemically inert thermoplastic binder, as disclosed in US 4511442. These composite materials require special molds and powerful presses and are produced at very low rates. For these reasons, the price of these composites is high, thus offsetting the advantage of higher electrical resistance and processability than pure graphite. It has been proposed to represent the hydrogen evolving cathode by an oxygen consuming cathode. This provides the advantage of a lower cell voltage, which in turn reduces the power consumption to 1000-. This reduction in energy consumption ultimately makes the electrolysis process attractive. However, although this system has been tested on a laboratory scale, its use on an industrial scale has not been reported to date. Another proposal has recently been made, in PCT publication WO95/44797(Du PontDe Nemours and Co.) in fact disclosing the electrolysis of gaseous hydrochloric acid obtained from plants for the production of isocyanates or fluorinated or chlorinated compounds. After suitable filtration to remove possible organic matter and solid particles, the hydrochloric acid is sent to an electrolytic cell, which is divided into two chambers with perfluorinated ion exchange membranes. The anode compartment has a gas diffusion electrode made of a porous membrane containing a suitable catalyst in intimate contact with an ion exchange membrane. Hole enlargement of gaseous hydrochloric acid through electrodeDiffuse to the membrane-catalyst interface where the hydrochloric acid is converted to chlorine. The cathode compartment also has an electrode in intimate contact with the ion exchange membrane, which is capable of generating hydrogen gas. The water stream removes hydrogen gas produced in the form of bubbles and helps control the temperature of the cell. However, under certain operating conditions, particularly during shutdown and start-up, the aqueous phase produced in the anode compartment contains a high concentration of hydrochloric acid, 30-40%. Therefore, this process also requires highly corrosion-resistant materials, possibly only graphite is suitable, and therefore also involves high investment costs, as mentioned aboveAs discussed above.

It is an object of the present invention to overcome these disadvantages of the prior art, and in particular to overcome them with the novel method of electrolysis with aqueous hydrochloric acid disclosed, the electrolysis cell of which has a gas diffusion cathode for the supply of oxygen. The method is characterized by high mechanical reliability and low investment costs.

The invention relates to a method for the electrolysis of aqueous hydrochloric acid, wherein the aqueous hydrochloric acid is fed to an anode compartment of an electrochemical cell, the anode compartment having an anode made of a corrosion-resistant substrate coated with an electrocatalytic coating for generating chlorine. Suitable substrates are laminates of graphitized carbon such as PWB-3(USAZoltek commercialised) or TGH (JP Toray commercialised) and expanded metal made of titanium, titanium alloys, niobium or tantalum. The electrocatalytic coating can be made of oxides of the platinum group metals or mixtures with optionally added stabilizing oxides such as titanium oxide or tantalum oxide. The cathode compartment is separated from the anode compartment by a perfluorinated ion exchange membrane of the cationic type. Suitable membranes are commercialized by Du Pont under the trade name Nafion^®Particularly Nafion 115 and Nafion 117 membranes. Similar products that can also be used are commercialized by Asahi Glass co. The cathode chamber has a gas diffusion cathode supplied with air, oxygen-enriched air or pure oxygen. The gas diffusion cathode is made of an inert porous substrate having a porous electrocatalytic coating on at least one side. For the purpose of facilitating the release of water produced by reaction between oxygen and protons transported from the anode compartment through the membrane, for example by embedding polytetrafluoroethylene particles in the catalyst layer, it is also possible to embedThe cathode is rendered hydrophobic throughout the porous substrate. The substrate is typically made of a porous laminate or a graphitized carbon cloth such as TGHToray or PWB-3 Zoltec. The electrocatalytic layer contains a platinum group metal or an oxide thereof (either by itself or in a mixture) as the catalyst. The choice of the optimum composition should take into account both the favourable reaction kinetics for the reaction of oxygen and the good resistance to the acidic conditions present in the electrocatalytic coating due to the diffusion of hydrochloric acid from the anode compartment through the membrane and the high potential of oxygen. Suitable catalysts are platinum, iridium, ruthenium oxide, either by themselves or supported on a carbon powder having a high surface area, such as Vulcan XC-72 (commercially available from Cabot Corporation). The gas diffusion cathode may be provided with a film of ionomer-containing material on the side facing the separator. The ionomer-containing material preferably has a composition similar to the material forming the ion exchange membrane. The gas diffusion cathode is brought into intimate contact with the ion exchange membrane under the action of heat and pressure, for example by pressing the cathode for a suitable period of time at a controlled temperature, pressure, before being placed in the electrolytic cell. In view of lower costs, it is preferred that the cathode and the diaphragm are placed in the electrolytic cell as separate pieces by fitting between the anode and cathode chambersThe combined pressure difference keeps them in contact (anode chamber pressure is higher than cathode chamber pressure). It has been found that satisfactory results are obtained with a pressure difference of 0.1-1 bar. With lower pressure differentials, the performance is significantly reduced, while with higher pressure differentials, the performance is marginal. As mentioned in the first alternative, the pressure difference is nevertheless useful when the cathode is pre-pressed against the membrane, since it is possible to cause separation between the cathode and the membrane over time, due to the capillary pressure generated in the pores by the water produced by the oxygen reaction. In this case, this pressure difference ensures a suitable intimate contact between the cathode and the membrane also in the separate regions. The pressure differential can only be applied when the cathode chamber is fitted with a rigid structure suitable for uniformly supporting the membrane-cathode assembly. Such structures are for example made of porous laminates with suitable thickness and good planarity. In a preferred embodiment of the invention, the porous laminate consists of two layers: with a first layer of expanded metal having a large mesh and the necessary thickness (so as to provide the necessary rigidity)) And a second layer consisting of a thinner porous metal mesh (making more contact points with the gas diffusion electrode) of smaller mesh than the first layer. In this way it is possible to easily and inexpensively solve the problem of the different requirements of the cathode structure which differ greatly, namely the rigidity and the multiple contact points against the surface of the gas-diffusion cathode and in close contact with the membrane, the former implying a large thickness and the latter a small hole or mesh, the easy access of oxygen and the rapid removal of the water formed by the reaction of oxygen, which objectives are only achieved with a small thickness.

The anodic and cathodic compartments of an electrochemical cell are defined on one side by an ion exchange membrane and on the other side by a conductive wall having suitable chemical resistance. This feature is evident for the anodic compartment to which hydrochloric acid is added, while it is also necessary for the cathodic compartment. In fact, it has been noted that, with the perfluorinated membranes mentioned above, the water resulting from the reaction of oxygen, i.e. the liquid phase collected at the bottom of the cathodic compartment, contains 5 to 7% by weight of hydrochloric acid.

The invention will now be described with reference to figure 1, which figure 1 is a diagrammatic longitudinal section through an electrochemical cell according to the invention. The cell comprises an ion exchange membrane 1, a cathode compartment 2, an anode compartment 3, an anode 4, an acid feed port 5, a discharge port 6 for spent acid and produced chlorine, walls 7 defining the anode compartment, a gas diffusion cathode 8, a cathode support member 9 having a thick perforated metal sheet or mesh 10 and a thin perforated metal sheet or mesh 11, an air or oxygen-enriched air or pure oxygen feed port 12, a discharge port 13 for acid water and possibly excess oxygen generated by the oxygen reaction, walls 14 defining the cathode compartment, and

circumferential gaskets

15 and 16.

In industrial practice, the electrochemical cells shown in figure 1 are generally illustrated according to a structure, i.e. so-called "filter-press" devices are combined in a certain number to constitute an electrolysis device, which is the equivalent of a chemical reactor. In the electrolysis apparatus, the respective electrolysis cells are electrically connected in parallel or in series. In the parallel arrangement, the cathode of each cell is connected to the negative pole of the rectifier by a conductive strip, and each anode is likewise connected to the positive pole of the rectifier by a conductive strip. In contrast, in a series arrangement, the anode of each cell is connected to the cathode of the next cell, and there is no need for a conductive strip as in a parallel arrangement. This electrical connection can be by means of suitable connectors which provide the necessary electrical continuity between the anode of one cell and the cathode of the adjacent cell. When the anode material and the cathode material are the same, they can be simply connected by a single wall, serving to define the anode compartment of one cell and the cathode compartment of the adjacent cell. This particularly simplified structure is used for an electrolysis apparatus for electrolyzing an aqueous hydrochloric acid solution using the prior art. In fact, in the described technology, graphite is used for the anode and cathode compartments as the only structural material. However, such materials are not very reliable due to their inherent brittleness, and are difficult and time consuming to process.

As already mentioned, pure graphite can be replaced by composites of graphite and polymers, in particular fluorinated polymers, which are softer but even more expensive than pure graphite. No other materials were used in the prior art. Of particular interest is the use of titanium which is characterized by an acceptable price, which can be produced in thin plates, which are easy to manufacture and weld, and which is also resistant to aqueous hydrochloric acid containing chlorine, which is the typical anodic environment in operation. However, titanium is susceptible to corrosion in the presence of chlorine and electric current, a typical situation that occurs during initial start-up and in all cases when the current is suddenly interrupted abnormally. In addition, when the prior art is used, electrolysis is performed without a gas diffusion cathode to which air or oxygen is supplied. Therefore, the cathodic reaction is the evolution of hydrogen gas, which, in the presence of hydrogen, is hydrogen embrittlement when titanium is used as the material of the cathodic compartment.

It has surprisingly been found that by making certain improvements to certain prior art electrolysis processes, it is possible to use titanium and titanium alloys, such as titanium-palladium (0.2%) alloys, as the structural material of the anode and cathode compartments, thus enabling simple and inexpensive construction of electrolysers entirely from metal.

The improvement disclosed by the invention is as follows: the oxide is added to the aqueous hydrochloric acid solution. The compound must be maintained under oxidizing conditions at all times by the action of chlorine, and not necessarily significantly reduced when in contact with a gas diffusion cathode. These requirements are met when the redox potential of the oxide is higher than the hydrogen discharge potential which, under strongly abnormal conditions, may occur at the gas diffusion electrode. This potential limit in the acidic liquid present in the pores of the gas diffusion cathode is 0 volts on the NHE (standard hydrogen electrode) scale. Acceptable values of redox potential are 0.3-0.6 volts NHE. Ferric and cupric iron may generally be added to the acid, but the invention is not intended to be so limited. Ferric iron is particularly preferred because it does not poison the gas diffusion cathode after it reaches and migrates through the membrane. The most preferable concentration of the trivalent iron is 100 to 10000ppm, preferably 1000 to 3000 ppm. The use of gas diffusion cathodes fed with air, oxygen-enriched air or pure oxygen. The maximum concentration of hydrochloric acid in the electrolysis unit was kept at 20%. The temperature is limited to about 60 ℃. Optionally, an alkali metal salt is added to the aqueous hydrochloric acid solution, preferably an alkali metal chloride, such as sodium chloride in the simplest case.

The reason for the improvement can be explained as follows: the addition of ferric iron or other oxides having similar redox potentials. Even in the absence of current or chlorine, the titanium remains in a passivated condition, i.e., corrosion resistant, due to the protective oxide film formed by the action of the oxide. This is the typical case when the cell is on and when the cell is shut down due to a sudden interruption of current for emergency reasons. During operation, the current and chlorine dissolved in the hydrochloric acid solution increase the effectiveness of the oxide, enhancing the passivation effect. When the redox potential of the oxide is sufficiently high, at least 0 volts NHE, preferably 0.3 to 0.6 volts NHE and when its concentration exceeds a certain limit, the oxide may form a protective oxide. In the particular case of ferric iron, the minimum concentration is 100 ppm. However, to achieve greater reliability while effectively protecting the cathode chamber, this concentration is preferably maintained at 1000-3000ppm, as discussed below. The necessary concentration of the oxides in the hydrochloric acid circulating in the anodic compartment of the electrolyzer can be controlled by measuring the values of the redox potential by means of an electrochemical probe or by means of amperometric measurements, as is well known in the electroanalytical art, forAre readily available for both probes and commercial instruments. The use of a gas diffusion cathode. With such a cathode, the cathode reaction reacts between oxygen and protons migrating from the anode chamber through the membrane to produce water. As mentioned above, the water produced is a strong acid as hydrochloric acid migrates through the membrane, wetting the walls of the cathodic compartment as a liquid phase. This acidity can be between 4 and 7%, depending on the operating conditions. Therefore, the cathode chamber is also strongly corrodedUsed, even below the typical corrosive effects of the anode chamber. The acidic liquid phase also contains an oxide that is added to the hydrochloric acid solution circulating in the anode compartment. The oxide, especially if in the form of cations (as is the case with ferric iron), migrates through the membrane due to the effect of the electric field and accumulates in the reaction-forming water in the pores of the gas diffusion cathode. Under the same operating conditions, the concentration of the oxidizing compound in the acid reaction-forming water depends on the concentration of the oxidizing compound in the hydrochloric acid solution circulating in the anode compartment. As mentioned previously, if the latter is maintained at a sufficiently high value, for example at 1000-3000ppm in the case of ferric iron, the concentration in the water of formation of the cathodic reaction also reaches a value sufficient to safely passivate the titanium, even when the acidity reaches a value of 4-7%. On the other hand, the use of a gas diffusion cathode eliminates the cathodic reaction that releases hydrogen, which is extremely dangerous for titanium, which can cause hydrogen embrittlement and can destroy corrosion-resistant protective oxides. Once the conditions necessary for the formation of the titanium protective oxide are obtained by the oxide in the hydrochloric acid solution circulating in the anodic compartment and in the acid water in the cathodic compartment, it is necessary to avoid other operating conditions that could damage this condition. It has now been found that suitable safety conditions are obtained when the operating temperature does not exceed 60 ℃ and the maximum concentration of hydrochloric acid in the solution circulated through the anodic compartment is 20% by weight. It has also been observed that the circulation of the hydrochloric acid solution in the anodic compartment effectively removes the heat generated by the joule effect in the solution and in the membrane, as well as by the electrochemical reaction. With moderate flow rates of hydrochloric acid, e.g. 100 l/h.m²The diaphragm makes it possible to maintain the temperature within a predetermined range of 60 ℃ and the current density can reach 3000-4000A/m². Alkali metal salts, especially sodium oxideAdded to the hydrochloric acid solution circulating in the anode compartment, this addition being carried out in order to combine the proton-influenced current transport with the alkali metal cation-influenced current transport, in particular sodium ions. This combined current transport, if properly balanced, neutralizes most of the acidity of the cathode reaction water present in the cathode compartment. The acidity can be reduced to 0.1-1%, 4-7% without adding alkali metal salt. Under the specific condition of sodium chloride, 20-50 g/L of sodium chloride is added into a 20% hydrochloric acid solution, so that the acidity of water generated in a cathode reaction is obviously reduced, and the titanium is further stabilized to a certain extent. These mild conditions also slow the leaching rate of certain catalysts that may be added to the gas diffusion cathode.

During testing with the electrochemical cell shown in fig. 1, it has been demonstrated that the above conditions, i.e. addition of oxide, control of temperature, maintenance of maximum concentration of circulating hydrochloric acid and use of gas diffusion electrodes, make it possible to use titanium for the construction of the anodic and cathodic compartments, which has long-term reliability with respect to corrosion. The only disadvantage is that occasionally fissured zones are found, i.e. where the titanium cannot come into any contact with the liquid phase containing the oxide. A typical example is the circumferential flanges of the anode and cathode compartments, corresponding to the gasket area. This problem is solved by applying a coating containing a platinum group metal or oxide or a mixture thereof, optionally also mixed with a stabilizing oxide (such as titanium oxide, niobium oxide, zirconium oxide and tantalum oxide) to the crevices, mainly to the circumferential flanges and the respective interfaces. Typical examples are mixtures of equal molar ratios of ruthenium oxide and titanium oxide.

Another more reliable solution is to use titanium alloys instead of blunt titanium. Of particular interest from a price and availability point of view is the titanium-palladium (0.2%) alloy. As is known in the art, such alloys are particularly resistant to crevice corrosion and are completely unaffected by corrosion in areas that have free contact with oxides, as explained previously.

Examples

As regards the performances of the electrochemical cell described above, FIG. 2 shows the cell electricity obtained according to the technique (1) of the invention and the prior art (2)The relationship between voltage and current density. The anode and cathode compartments made of titanium-palladium (0.2%) alloy (titanium-based alloy containing 0.2% by weight of palladium known to the expert in the field) (see

numerals

2 and 3, 7 and 14 of figure 1) are fitted with circumferential gaskets made of ethylene/propylene/diene copolymer (EPDM) elastomer. The anode chamber was equipped with an anode made of a porous titanium-palladium (0.2%) alloy plate, forming an uneven mesh, 1.5mm thick, oval holes with diagonal lines of 5 and 10mm respectively, and an electrocatalytic coating made of a mixture of ruthenium oxide, iridium oxide and titanium oxide (4 in fig. 1). The cathode chamber had a 0.2% titanium-palladium thick screen (1.5 mm thick with oval holes with diagonal lines of 5 and 10mm, respectively); a thin screen of 0.2% titanium-palladium (

parameters

9, 10 and 11 in fig. 1) (0.5 mm thick with oval holes with 2 and 4mm diagonal lines, respectively) was spot welded thereto. The thin screen had an electrocatalytic coating made of platinum-iridium alloy. However, it will be apparent to those skilled in the art that several types of other corrosion resistant conductive coatings may be used. Dual mesh structure supported a gas diffusion cathode consisting of E-TEK-USA commercial ELAT electrode (30% Pt/Vulcan XC-72 activated carbon, 20 g/m total²Noble metal) having a perfluorinated ionomer membrane (8 in figure 1) on the opposite side of contact with the double screen structure. Two chambers with Nafon supplied by Du-Pont-USA^®117 the membrane is separated (1 in fig. 1). The anode compartment is fed with 20% aqueous hydrochloric acid and the cathode compartment with pure oxygen at a slightly above atmospheric pressure, at a flow rate corresponding to a stoichiometric excess of 20%.A pressure difference of 0.7 bar was maintained between the two chambers. The temperature was maintained at 55 ℃. Ferric chloride was added to the hydrochloric acid to give a ferric concentration of 3500 ppm. The liquid withdrawn from the bottom of the cathode chamber was a 6% aqueous hydrochloric acid solution containing about 700ppm of ferric iron.

The cell operation lasted for 350 hours with various intermediate shutdowns and prolonged periods of use in the presence of standing acid. No performance degradation was observed, and no corrosion was observed even in the raised edge portion of the circumferential gasket. The outlet liquid was further analyzed and no appreciable traces of titanium were detected.

Claims

1. A process for the electrolysis of aqueous hydrochloric acid solutions for the production of chlorine, which is carried out in an electrolysis apparatus consisting of at least one electrochemical cell having a cathode compartment and an anode compartment, which are separated by a cationic, corrosion-resistant ion-exchange membrane, each of the cathode compartment and the anode compartment being equipped with a gas-diffusion cathode and an anode made of an inert substrate provided with an electrocatalytic coating for the evolution of chlorine, at least the gas-diffusion cathode and the membrane being in intimate contact, the cathode compartment also having an oxygen-containing gas feed opening and a reaction product water discharge opening, the anode compartment having an inlet for the aqueous hydrochloric acid solution to be electrolyzed and an outlet for the aqueous hydrochloric acid solution waste and the chlorine evolved, characterized in that the concentration of the aqueous hydrochloric acid solution to be electrolyzed is a maximum of 20% by weight and the temperature of the aqueous hydrochloric acid waste solution does not exceed 60 ℃, which is carried out in an electrolysis cell in which the anode compartment and, and having at least 100ppm of an oxide having an oxidation-reduction potential in aqueous hydrochloric acid to be electrolyzed at least equal to 0 volt standard hydrogen electrode.

2. The method of claim 1, wherein the redox potential is 0.3 to 0.6 volt standard hydrogen electrode.

3. A method according to claim 1, characterized in that said oxide is ferric iron.

4. A method according to claim 3, characterized in that the concentration of ferric iron is maintained in the range of 100 to 10000 ppm.

5. A method according to claim 4, characterized in that said concentration is maintained in the range of 1000 to 3000 ppm.

6. A method according to claim 4 or 5, characterized in that the concentration is controlled by means of an electrochemical probe or amperometric measurement.

7. The method according to claim 1, characterized in that the temperature of the spent aqueous hydrochloric acid solution is controlled by adjusting the flow rate of the aqueous hydrochloric acid solution to be electrolyzed.

8. A method according to claim 7, characterized in that the flow rate is 100 liters/hr-m²A diaphragm having a current density of 3000 to 4000A/m²A diaphragm.

9. The method of claim 1, wherein the aqueous hydrochloric acid solution to be electrolyzed is additionally supplemented with an alkali metal salt.

10. The method according to claim 9, wherein the alkali metal salt is sodium chloride at a concentration of 20 to 50 g/l.

11. A process according to claim 1, characterized in that the titanium or titanium alloy used as construction material for the anode and cathode compartments has a protective electrocatalytic coating in the crevice region of both compartments.

12. The method of claim 11, wherein said protective coating is made of platinum group metals and their oxides, used alone or in combination, optionally with the addition of a stabilizing oxide selected from the group consisting of titanium oxide, niobium oxide, zirconium oxide, tantalum oxide.

13. The method of claim 12, wherein said protective coating is made from a mixture of equimolar amounts of ruthenium oxide and titanium oxide.

14. A method according to claim 1, characterized in that the structural material is a titanium-palladium alloy containing 0.2% by weight of palladium.

15. The method of claim 1, wherein the surface of the gas diffusion cathode in intimate contact with the ion exchange membrane has a film of corrosion resistant ionomer-containing material.

16. The process of claim 1 wherein said intimate contact between the gas diffusion cathode and the ion exchange membrane is achieved by adhesion under heat and pressure prior to installation in said electrolyzer.

17. The process of claim 1 wherein the anode compartment is at a higher pressure than the cathode compartment.

18. A process according to claim 17 wherein the pressure differential between the anode and cathode compartments is maintained in the range of 0.1 to 1.0 bar.

19. The process of claim 17 wherein said gas diffusion cathode and ion exchange membrane are supported by a rigid porous structure having a plurality of contact points with opposite surfaces of the gas diffusion cathode in intimate contact with the membrane, said structure being in the cathode compartment.

20. The method of claim 19, wherein said structure is made of a rigid thick perforated metal sheet or screen and a thin perforated metal sheet or screen, said thick and thin perforated metal sheets or screens being made of titanium or titanium alloy, said thin perforated metal sheet or screen having a corrosion resistant conductive coating thereon.